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61.
The enzymatic polymerization to provide synthetic chondroitin and its derivatives is reported here, the first example of such in vitro synthesis to date. N-Acetylchondrosine (GlcAbeta(1-->3)GalNAc) oxazoline (1a) and its derivatives (1b-1f) were designed and synthesized as novel transition state analogue substrate monomers for catalysis by hyaluronidase. Hyaluronidase is a hydrolysis enzyme of chondroitin that also catalyzes the formation of repeated glycosidic bonds in in vitro synthesis, rather than in the catabolic direction. Monomers of 2-methyl (1a), 2-ethyl (1b), and 2-vinyl (1f) oxazoline derivatives were polymerized using this enzyme, via ring-opening polyaddition with total control of regioselectivity and stereochemistry. These reactions provided the corresponding synthetic chondroitin (natural type; N-acetyl, 2a) and the derivatives (unnatural type) with N-propionyl (2b) and N-acryloyl (2f) functional groups at the C2 position of all the galactosamine units, in good yields. Monomers of 2-n-propyl (1c) and 2-isopropyl (1d) oxazoline derivatives were polymerized to produce 2c and 2d in low yield. The 2-phenyl oxazoline derivative (1e) did not afford any enzyme-catalyzed products. M(n) values of 2a and 2b reached 4800 and 4000, respectively. The M(n) value of 2a corresponds to that of the naturally occurring chondroitin. Thus, hyaluronidase catalysis allows the in vitro production of not only natural type but also the formation of unnatural type chondroitins. 相似文献
62.
Bis(carbazolylphenyl) and bis(diphenylaminophenyl) derivatives of 1,6-methano[10]annulene, which is luminescent material and contains seven-membered rings, are synthesized. The bis(phenylcarbazole) derivative 3 have high melting point and glass transition temperature. Electroluminescence characteristics of organic light-emitting diodes using these methano[10]annulenes were investigated. 相似文献
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64.
Murahashi S Komiya N Terai H Nakae T 《Journal of the American Chemical Society》2003,125(50):15312-15313
RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium cyanide under molecular oxygen (1 atm) at 60 degrees C gives the corresponding alpha-aminonitriles, which are versatile synthetic intermediates of various compounds such as amino acids and unsymmetrical 1,2-diamines, in excellent yields. This reaction is clean and should be an environmentally benign and useful process. 相似文献
65.
Grafting of tetrafluoroethylene onto polyethylene was carried out by a pre-irradiation technique. It was found that grafting proceeds very rapidly at -35°C in the liquid phase of tetrafluoroethylene. Takathene, which was prepared by a radiation process at Takasaki Radiation Chemistry Research Establishment, was found to be most suitable for grafting compared to other polyethylenes. The specific surface is extremely high in the Takathene, and this may be the most important reason for the high grafting speed. On the other hand, IR measurements of the grafted copolymers showed a characteristic absorption band at 1110 cm-1 which may be attributed to the structure of the grafting (branching) position. It was also found that grafted polytetrafluoroethylene can be crystallized during grafting. This is the first case of grafted polymers being in a crystalline state. 相似文献
66.
H. Uchida Y. Masuda R. Fujikawa A.V. Baryshev M. Inoue 《Journal of magnetism and magnetic materials》2009,321(7):843-845
A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed. 相似文献
67.
68.
Gururaj M. ShivashimpiShyam S. Pandey Rie WatanabeNaotaka Fujikawa Yuhei OgomiYoshihiro Yamaguchi Shuzi Hayase 《Tetrahedron letters》2012,53(40):5437-5440
Aiming toward the development of far-red sensitive organic dyes, unsymmetrical squaraine dye bearing direct cyanoacrylate functionalized indole ring has been synthesized and characterized along with its utilization as photosensitizer for dye-sensitized solar cells. Upon dye-sensitized solar cell fabrication, this sensitizer exhibits its potentiality as a good far-red sensitive dye having photoconversion efficiency of 5.03% under the simulated solar irradiation at AM 1.5 conditions. This opens up further possibility to design efficient far-red sensitive dyes by judicious implementation of suitable donor moieties with extended π-conjugation. 相似文献
69.
70.
Kobayashi S Ohmae M Ochiai H Fujikawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(23):5962-5971
Hyaluronidase (HAase) catalyzes multiple enzymatic polymerizations with controlling regio- and stereoselectivity perfectly. This behavior, that is, the single enzyme being effective for multireactions and retaining the enzyme catalytic specificity, is not usual, and hence, HAase is a supercatalyst. Various sugar oxazoline monomers prepared based on the concept "transition-state analogue substrate" were successfully polymerized and copolymerized with HAase catalysis, yielding natural and unnatural glycosaminoglycans. 相似文献